Thiophenated ketones and mineral oil compositions containing the same



Patented Mar. 30, 1954 UNITED STATES PATENT OFFICE THIOPHENATED KETONES AND MINERAL OIL COMPOSITIONS CONTAINING THE SAME Orland M. Reilf and Alfred P. Kozacik, Woodbury, N. J., assignors to Socony-Vacuum Oil g ompany, Incorporated, a corporation of New ork N Drawing. Application December 29, 1949, Serial No. 135,834

4 Claims. (01. 252-482) 1 2 This invention relates to improved lubricating dodecenyl ketone, tetradecyl octadecenyl ketone, compositions. More particularly, the invention is ditetradecenyl ketone, dioleyl ketone (oleone). concerned with mineral lubricating oil composi- The reaction between the unsaturated aliphatic tions containing thiophenated ketones as 0Xidaketone and the thiophene may be readily effected tion and corrosion inhibitors. as in the presence of a synthetic silica-alumina type As is well known, mineral lubricating oils tend catalyst. We have found that such a catalyst, to decompose, especially under heat and oxidizing containing, for example, about 87.5% (by weight) conditions, such as those encountered in use in of silica and about 12.5% of alumina is most satinternal combustion engines. The decomposition isfactory. We have found that by the use of such products formed in the oil are acidic in nature a catalyst no polymer products are formed as and exert a corrosive action upon the metal suroccurs by the use of other catalysts such as AlCla, faces being lubricated. The present invention ZnClz, or the like. In conducting the reaction, is concerned with a novel class of chemical comthe reactants and the catalyst are mixed together pounds which are highly effective in counterand heated at a temperature of from about 300 acting the tendency of lubricating oil to oxidize F. to about 600 F. for a period of from about 1 and thus corrode the metal surfaces. to about 15 hours. Generally, sufficient thiophene We have discovered that thiophenated aliphatic is employed in order to provide at least one mol ketones, produced by reacting aliphatic ketones of thiophene for each olefinic bond in the ketone having one or two monoolefinic aliphatic groups reactant. However, it is preferred to use an exwith thiophene, are excellent addition agents cess of thiophene, over the stoichiometrical for stabilizing mineral lubricating oils against amount. The reaction product is readily sepathe deleterious efiects of oxidation. rated from the catalystand unreacted thiophene It is, therefore, the primary object of this inby distillation and filtration. A monothiophenvention to provide lubricating oil compositions ated product of a diolefinic ketone may be precontaining these new anti-oxidant compounds. pared by using only a slight excess over 1 mol of Other objects will become apparent as the dethiophene per mol of the diolefinic ketone. Al-

scription of the invention proceeds. though the final product in this instance will As far as is known, the thiophenated aliphatic most probably contain minor amounts of dithioketones of this invention have not been known phenated ketone the monothiophenated product heretofore and are, therefore, considered to be can be readily separated from the dithiophenated new compositions of matter. product by fractionation. However, for the pur- As already indicated. the t cp d alipose of the present invention, such separation is p c ketones of the invention are produced not necessary since both the monoand dithiofrom unsaturated aliphatic ketonbs by thiophenaphenated aliphatic ketones are effective tition oi the olefinic bonds thereof. If the ketone oxidants for mineral lubricating 0i1s Accord 1s a diolefinic ketone, one or both of the olefinic ingly, a product containing a mixture of mono bonds may be thiophenated. and dithio phenated ketones may be used as such The ketones contemplated fol use m the for addition to the mineral lubricating oil.

ventlon conform to the general formula The reaction between the unsaturated ali phatic ketone and thiophene is considered to take 0 place at the olefinic bond (or bonds) of the kewherein the R's represent either an alkyl or an {one as follows:

alkenyl group, at least one being an alkenyl group.

By alkenyl we mean a monovalent aliphatic g HGCH f: radical having a double bond therein, for ex- C= H -0 ample, -CH2-CH=CI-ICH3. The ketone may r'r have from 4 up to about 35 carbon atoms and S C=CH may be either straightor branch-chained. As non-limiting examples of suitable ketones, there I may be mentioned methyl vinyl ketone (butenone), allyl acetone (5-hexen-2-one), mesityl oxide (4-methyl-3-penten-2-one) phorone (2,6- to give a mono-, or a dithioph'enated ketone proddimethyl-2,5-heptadien-4-one), octyl octenyl uct, depending upon whether' the unsaturated ketone, dioctenyl ketone, vinyl wax ketone, octyl ketone contains one or two alkenyl groups and 3 upon the amount of thiophene used in the reaction.

The thiophenated aliphatic kctones of the invention may, therefore, be represented by the general formula wherein, X is a thienyl group, R is an alkyl radical having from 1 to carbon atoms, m is a whole number from 0 to 10 and n is a whole number selected from 0 and 1, the total number of carbon atoms in said thiophenated ketone being from i to about 35, exclusive of thienyl carbons.

In order to illustrate the method of preparation of our thiophenated aliphatic ketones and thienyl oleone obtained in Example 1, above, was blended in minor proportions with a typical mineral lubricating oil, viz. Olean 10. This is a solvent-refined oil of S. U. V. at 210 F. The blends were then tested by means of the Lauson Engine Oxidation Stability Test. This test determines oil deterioration as measured by increase in neutralization number (N. N.). The procedure is as follows: The test is carried out in a single cylinder, liquid cooled, Lauson engine operated continuously over a time interval of 36 hours. During the test, the cooling medium is held at a temperature of about 212 F. and the oil temperature at 250-260 F. The engine speed is maintained at 1815 R. P. M. The N. N. and viscosity of the test oil and the preceding blank oil are reported for 12, 24 and 36 hours. The results of these tests were as follows:

Kin. Vis. 210 F., cs. Neutralization Number Cone. (by wt.) in Olean 10 12 Hrs. 24 Hrs. 36 Hrs. 12 Hrs. 2i Hrs. 36 Hrs.

Previous Blank... 5. 91 6. 68 8. 57 1.1 4. 0 l1. 6 2}% Product I. 6.02 6. 29 0. 76 l. O 1. 6 3. 6 Previous Blank"-.. 5. 97 7. 19 l0. l0 1. 7 5. l3 l4. 8 5% Product I 6. 03 6. 24 6. 54 0. 5 0. 9 2. 1

their effectiveness as antioxidants in lubricating oil compositions, the following specific examples and test results are given.

EXAMPLE I Three hundred and twenty grams (0.638 mol) of oleone (iodine No. '78), 198 grams (2.36 mols) of thiophene and 51 grams of synthetic silicaalumina catalyst were placed in a 2.8 liter shaker bomb and heated at 500 F. for 7 hours. After the bomb had cooled to room temperature, the contents were removed by addition of benzene, the catalyst was removed by suction-filtration through a layer of filter-aid. The filtrate was placed in a distillation flask, the benzene distilled off, the product remaining was topped to 275 at 7 mnr, to make certain no light products remained. The residual product amounted to 394 grams; analysis showed 7.72% sulfur (theo.::7.38% for a product of dithiophenated oleone of 78 iodine number). This product (product I) is, therefore, considered to be substantially entirely dithiophenated oleone, i. e.

EXAMPLE 11 Three hundred and twenty grams (.638 mol) of oleone (iodine number theor. 101; found 101) 198 grams (2.36 mols) of thiophene, and 51 grams of a synthetic silicate catalyst were heated and processed as above. The residual product had a sulfur content of 8.31% as compared to the theoretical value of 9.55% for the dithiophenated product of oleone of 101 iodine number. As in Example I, this product (product II) is considered to be essentially dithiophenated oleone.

Antioxidant action The following test results will serve to illustrate the effectiveness of the thiophenated ketone type compounds of the invention, as antioxidants in mineral lubricating oils. The di- That the additives of the invention very effectively prevent oxidation of mineral lubricating oils under conditions of actual use in an internal combustion engine is shown by the low viscosity and N. N. of the blended oils as compared to the unblended oils.

The amount of thiophenated aliphatic ketone added to the mineral oil will vary somewhat with the intended application of the oil composition, and generally will be from about to about 10% by weight. However, the preferred amount is from 2 to 5%. It is further contemplated that the product compounds be incorporated in the oil in greater amounts, i. e. above about 10%, to provide oil concentrates for marketing. These concentrated compositions have the advantage of affording a readily soluble form of the additive materials for dilution with additional amounts of oil prior to actual use.

The oils in which our new addition agents are used, or the oil concentrates, may also contain other additives, designed to improve the character of the oil in other respects, such as detergency, V. I., pour point, etc.

Although the principles of this invention have been illustrated herein by means of certain specific examples and tests, it is not intended that the scope of the invention be limited thereby, but only as indicated in the following claims.

We claim:

1. A mineral lubricating oil containing a minor proportion, sumcient to inhibit the deleterious effects of oxidation thereof, of a thiophenated aliphatic ketone represented by the general formula X o x 11 wherein, X is an unsubstituted thienyl group, R is an alkyl radical having from 1 to 10 carbon atoms, m is a whole number from 0 to 10 and n is a whole number selected from 0 and 1, the total number of carbon atoms in said thiophenated ketone being from 4 to about 35, exclusive of thienylcarbons.

2. Amineral lubricating oil containing a minor 5 proportion, from about 0.1% to about 10%, of a thiophenated aliphatic ketone represented by the general formula KB XH wherein, X is an unsubstituted thienyl group, R is an alkyl radical having from 1 to 10 carbon atoms, m is a whole number from 0 to 10 and n is a whole number selected from 0 and 1, the total number of carbon atoms in said thiophenated ketone being from 4 to about 35, exclusive of thienyl carbons.

3. A mineral lubricating oil containing a minor proportion, sufficient to inhibit the deleterious effects of oxidation thereof, of the compound I: S S

4. A mineral lubricating oil containing a minor proportion, sufiicient to inhibit the deleterious effects of oxidation thereof, of the compound ORLAND M. REIFF. 

